JPS6059096A - Fiber continuous plating device and method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to metallized filaments and methods and apparatus for making them.

Non-metals and metalloids in the form of monofilaments, threads, threads, cloaks, cloth and chopped strands, e.g.
carbon, boron, silicon carbide, polyester, nylon,
Aramid, cotton, rayon, etc. are known to be useful in reinforcing generic and organic polymeric materials. Articles made of such fiber-reinforced metals or plastics are used for low strength applications in aircraft, aviation, office equipment, sporting goods, and many other areas.
It is widely used in replacing heavy components composed of common materials such as alumina J., steel, titanium, vinyl polymers, nylon, polyester, etc.

A common problem in the use of such filaments, and also glass, asbestos, etc., is that there appears to be a lack of ability to transfer the high filament properties to the materials with which ultimate and intimate contact is to be made. For wood quality, high strength filaments are used;
is only mechanically trapped in the l, and the resulting complex separates or breaks when pulled with unexpectedly low forces.

These problems have been partially overcome by depositing at least one layer of metal on the individual filaments L-, L-, and then incorporating them into a bonding material 1, such as metal or plastic. Deposition of metals is accomplished by applying metal to the fibers, e.g., in a vacuum, as described in U.S. Pat. No. 4,132,828, and as described in U.S. Pat. No. 3,894,677. by electroless deposition of, for example, nickel, from a chemical bath into graphite filaments, as described in US Pat. No. 3,622,283 (Sara et al.
) and U.S. Patent No. 3,807,996 (S a r
This was achieved by electrodepositing, for example, nickel onto the carbon fibers J2 as described in a). When a metallized filament is twisted or sharply bent in such a procedure, a very substantial φ of said metal flakes off or falls off as powder. When such metallized filaments are used for reinforcing metals or polymers, the ability to resist compressive stress and tensile strength is much inferior to what would be expected from the law of mixtures, and this fact The I! between filament and metal coating is less than efficient reinforcement. , strongly suggests that this is due to inferior binding of 'I.

'll1i: If we choose plating and use an amount of voltage such that it is more than the amount of voltage that is achieved to simply dissolve (reduce) the electro-conductive metal on the surface J of the filament, It has now been discovered that an excellent bond is formed between the filament and the metal layer. The strength is such that when the metal-coated filament is bent sharply, the coating breaks but does not flake off. That'-
One continuous length of such metallized filaments can be tied or twisted without loss of metal to flakes or powder. It is believed that the high voltage provides or promotes uniform nucleation of the electrodeposable metal on the filament and overcomes the effects of screening or blocking material adsorbed onto the filament surface.

Although it requires a certain φ current to electrodeposit metal on the filament surface, increasing the voltage to increase the amperage may burn the filament, which interferes with the continuous method. U.S. Time 6th 3rd, 807, 99
No. 6 (Sara) describes a method of continuously nickel plating graphite yarn, but only 2
．． Using a plating current of 5 amps 7 and a long residence time 1, e.g. 14 minutes, therefore using a low, common voltage. In another method described in British Patent No. 1.272.777, M! By passing the individual fibers in the weito into a jet of electrolyte carrying the plating material, they are electroplated without burning, and the fiber bundles are maintained at a negative potential with respect to the electrolyte in the case of silver on graphite. , the potential between the anode and the fiber is a normal 3 volts.

The present invention provides an efficient device for promoting potential build-up between an anode and a continuous filament cathode. This is because increasing the voltage to obtain better metallized fibers is an important aspect of the present invention. Furthermore, since it allows the introduction of extra electrical energy into the system without burning the filament, the residence time is shortened and the production rate is greatly increased compared to prior art methods. As is clear from the detailed description below,
IJi provides high voltage plating, strategic cooling, efficient electrolyte-filament contact and high speed filament transport in various combinations, all of which improve production rates and Increase the amount of metallized filament. Such filaments find substantial use, e.g. in thermoplastic and thermoset materials for aircraft lightweight protection, EMI,/RF I shielding and other applications requiring electrical/electronic insulation. It can be used when incorporated into sexual formulations. Composites in which such filaments are arranged and dispersed in a substantially 11-row manner in a matrix of metal1, for example, composites of nickel-coated graphite in a matrix of lead or zinc, are lightweight and have compressive and tensile stresses. It is characterized by excellent resistance to The apparatus of the invention is also suitable for electroplating a normally non-conductive continuous filament, such as polyamide or cotton, if the adhesive conductive inner layer is first deposited, e.g. by chemical means, onto the non-conductive material. When doing so, the production rate and product quality can be increased.

The basic object of the present invention is to provide a fiber made from a conductive metalloid with a metal coating.

Another object of the present invention is to provide a method for carrying out electroplating of textiles under high voltage electroplating conditions.

Furthermore, it is an object of the present invention to provide a method for efficiently and rapidly coating fibers with a metal coating and facilitating cleaning and collection of the finished product.

A further object of the invention is to reduce the variation in plating thickness by 10
The objective is to provide fibers that are uniformly plated around the diameter to an extent less than %.

It is also an object of the invention to plate all fibers of the tow with the same width in the material, irrespective of whether the width of the tow is small or large, ie 3KN12KX12.

Another object of the invention is that the metal filaments, especially the metal-coated filaments, can be provided with abrasive properties to facilitate their incorporation with organic materials, and that the metal-coated fibers can be coated or matted. The object of the present invention is to provide a method capable of imparting desirable and necessary properties for weaving similar articles.

A further object of the invention is to provide a metal filament with lubricious properties.

Another object and further object of the present invention is to minimize irregular fibrils extending outward from the base fibers. An object of the present invention is to provide a metal coated high strength fiber.

Yet another object of the invention is to provide a metallized filament having a metal oxide surface layer.

Another object of the invention is to provide a composite, for example a laminate, consisting of metallized filaments with a surface treated by sizing and/or oxidation and an organic polymeric material.

It has been found that these and other objects are achieved through the use of high voltages in the apparatus and methods of the present invention.

In accordance with the present invention, an apparatus is provided in which multiple fibers can be efficiently plated on a metal surface simultaneously and thus cleaned and rolled up for use in a variety of end products.

The apparatus generally includes a pay-out assembly that can supply a large number of fibers to the electrolytic plating bath. Pretreatment includes sodium phosphate cleaning, rinsing, and acid washing. For plating applications for plating non-conducting fibers, pretreatment methods can also include roughening or polishing the fibers followed by chemical deposition of a thin metal interlayer. after that,
Electrolysis, in which the plating of textiles is carried out under conditions of high voltage (metal plating is carried out in a rapid manner by passing clean fibers through an electrolytic bath and contact rolls associated with the electrolyte bath). Means are provided for cooling the *i during its passage. Preferred means consist essentially of recirculating the electrolyte at strategic locations above the contact rollers and the fibers. It also includes a series of discrete electrolyte baths associated with separate rectifiers to facilitate variable current plating, where the current varies as a function of the resistance created by the plating on the fiber.

After plating is completed, the plated fibers are washed with water,
Steam and then dry.

The tightly bonded, high voltage, metal coated M& fibers produced by the apparatus and method of the present invention are extremely useful as reinforcing materials to provide improved m-fiber-resin matrix composites. In these end uses, the surface of the metallized fibers is sized so that they are easily tied or woven into mats or fabrics and are compatible with the matrix to which they are intended to be reinforced. It is further desirable that it be increased.

In accordance with this aspect of the invention, the post-treatment sizing method of the invention comprises coupling and sizing agents, such as aminosilanes, alone or together with softening and polymeric sizing agents, such as polyvinyl acetate. It is characterized by feeding a metal filament into combination with a medium. Further processing of this timber 2I is as follows:
It is also possible to pass the material through dispersants, fluxes, and/or external lubricating and sizing agents, such as polyethylene emulsions, after exiting the polymer sizing bath, or in combination with the latter bath. include. This entire method is called ``convenience'' nisizing. During intermediate steps or after the sizing step is completed, the fibers can be heated to dry and harden the m#N- size. Among its features, the invention also encompasses a method of surface quenching metal filaments under controlled conditions, either alone or in combination with sizing.

As a result of the low voltage electroplating process, a conventional line is provided that has means for synchronizing each of the process steps with the other steps. The high voltage environment is also provided with fingers of unequal length, and the anode hash, a part of which is insulated for protection from the electrolyte bath, thus specially designed Due to the anode arrangement, the contact roller reservoir contains a specially designed 'IM' tone.

The wash and electrolyte baths are specifically designed to maintain the electrolyte level and minimize the accumulation of used wash fluid.

Special rollers developed for use in unwinding further facilitate this method.

The method and apparatus of the present invention can be applied to nonmetallic fibers and semimetallic fibers*.
Efficient and complete -f-1 for metal plating fibers
Regarding providing 3k.

The method of the invention is based on the use of non-rich voltages and currents to achieve satisfactory plating. As a result of the low voltages and currents, equipment has been developed that can produce large volumes of plated material under conditions of high voltage.

In a preferred embodiment in which the particular fibers to be plated are carbon fibers or graphite fibers and the metal to be plated is nickel, the method of the invention and the apparatus particularly suitable for carrying out the method of the invention will be described. However, the method and apparatus of the present invention are suitable for virtually the entire spectrum of metal plating of non-metallic and semi-metallic fibers.

The overall method and diagram of the apparatus, excluding the unwinding assembly, is generally shown in FIG. The operation process consists of an unwinding assembly for dispensing a large number of fibers into one line per line, a tension roller 6, a pretreatment section 8, and a plating equipment 1.
0. It includes a wash station 12, a drying section 14 and a take-up reel 16.

More specifically, the preliminary processing 14 shown in FIG.
1I! ! 18 is a phosphorous-sodium cleaning compartment 26 and an associated washing tee.
) 28, washing compartment 30 and associated washing T-shape'it
'32 and 32A, hydrochloric acid compartment 34 and associated wash f
> T-tube 36, and wash section 38 and associated wash T-tubes 40 and 4OA, all of which are illustrated in FIG. Plating equipment 10 is comprised of multiple series of electrolyte vessels, illustrated as vessels 18, 20, 22 and 24 in FIG. 1, each of which is better illustrated in FIGS. 8 and 22. The current is supplied from separate rectifiers as shown in the figure. Washing section 12 is shown generally in FIG. 1 and is comprised of a tank and tee assembly similar to pre-processor 11 processing equipment. The arrangement of the cascade reservoir 42 and the T-shaped tubes 44, 44A and 44B directs the water and electrolyte cleaning solution to the fibers 2. Thereafter, clean water is passed through the fibers 2 in the washing section 46. The washing section 46 includes a tank and a wash f'I+T-shaped bamboo 48 and 4, as shown in more detail in FIG.
It has 8A. The washed fibers 2 pass through a section 50;
Here it is air injected in compartment 53 and then steam treated in compartment 55 to the common guide roller 5 and into the tension roller assembly 6. A guide rod 59 is provided for guiding the fiber 2 from the unwinding roller 54 to the associated guide roller 62.

As shown in FIG. 3, the guide roller 62 is
When multiple fibers 2 are fed into the system simultaneously to be processed and plated, they are aligned adjacently to each other to bridge the interference between the fibers 2.

The structure of unwind roller 54 is best shown in FIGS. 4 and 5. The unwinding roller 54 consists of a centrally located rod 66 having end bearings 68 and 70 and is arranged to receive a compression frame 64 formed from a button metal 72. There is. Practice has taught that four pieces of resilient wire 72 oriented at 90° will form a suitable frame for mounting commercial spools of most fibers. Bearing 68 is arranged to support rail 56 or rail 58 of unwinding assembly 4 .

The rod 166 sees a threaded end 76 passing through an opening in the rail 56 or 58. Attach the unwinding roller 54 using a screwdriver (not shown). The unwinding roller 54 is thus mounted in a cantilevered manner,
It has a free end bearing 70 that fits snugly onto the rod 66. Thus, when the wires 72 of the unwind roller frame are compressed, the bearings 70 are able to move laterally on the rods 66--1. Additionally, the frame button 72 has one tapered end 74. As a result of the taper in the frame wires 72 and the laterally driven bearings 70, the compression frame 64 is adjustable to accept spools of fiber of various diameters.

The unwinding assembly 4 feeds the fibers over guide rollers 5 to wetting rollers 80 and then to tension rollers 6. Wet tub 84 contains water. The water wets the fibers 2 and allows proper and more efficient cleaning and washing of the fibers 2 during pretreatment.

The tension roller 6 shown in FIG. 1 is shown more clearly in FIG.

The tension roller 6 consists of seven assemblies of five rollers 90, all of which are driven by a common source, e.g. a variable speed motor 92. I! It is driven via a connecting chain 87. Each roller 90 is attached to a shaft 89. A fixed gear 91 is also attached to the shaft 89t, and a chain 87 is disposed around the gear 91. Idler roller 97 is also positioned to engage chain 87. σcho variable speed motor 92
A gear 93 extending from the shaft 95 of drives the continuous chain 87 via a chain 101 and a gear 103 fixed to the shaft 89 of the roller 90 . At some point in the line of flow of the first plating contact roller, it is necessary to apply tension to the fibers 2. The plating contact roller and fiber 2 must be in intimate contact to facilitate operation at the high voltage and high current levels required for this process. In close contact, a low resistance is formed between the TA fiber 2 and the contact roller, and thus the high current passing through the circuit of the system overloads the fiber fA2.
d) will not destroy the fibers. Eventually, the tension roller assembly 6 is installed in the electroplating bath 18.20.22
．． 24 (FIG. 1) to provide tension.

On the other hand, the fibers should be subjected to as little drag as possible.

The tendency of m-fibers to separate and accumulate fluff at the surface
It is unique to The variable drive motor 92 is
Connections to all five rollers 90 provide the rollers with variable speed pawls at a speed equal to or less than the speed of the fibers 2.

At carefully controlled speeds, the necessary tension is provided without causing fuzz build-up on the fibers. The apparatus and method are designed to provide an assembly of tension rollers 6 in which tension rollers 90 move at a slower speed than the fibers. #
Tension in the fibers is maintained by varying the speed of tension roller 90 in response to visual determination of tension.

In accordance with the new and improved apparatus and method of the present invention,
The ta#I to be coated is first cleaned in the pretreatment section 8. The pretreatment provides an improvement consisting in providing a core fiber with a surface that is substantially free of adsorbed organic compounds that would interfere with the electrodeposition of metals. The surface is substantially free of adsorbed organic compounds and the organic compounds are in the core! It can be obtained by removal from 1lIn, for example, by solvent washing, by chemical cleaning, by high temperature cleaning, etc.

As used herein, the term "substantially free" refers to very small amounts of adsorbed organic compounds, i.e.
It means an amount that does not interfere with plating or contribute to non-uniform coating. Although it is very difficult to remove or avoid all traces, exposure of up to about 5% of the surface area of short lengths can usually be included and tolerated without significant injury. I can do it.

In one pretreatment, the surface is substantially free of adsorbed organic compounds, and substantially all of any such compounds are removed by contacting the core fiber with a solvent for such compounds. This can be achieved by One useful solvent is 1,1.1-trichloroethane. This is a common degreaser. Due to the high purity requirements of the cleaned fibers, the solvent must be frequently changed or purified.

In the preferred embodiment of FIG. 1, a surface substantially free of adsorbed organic compounds is obtained by removing substantially all of such compounds by contacting the fibers with an aqueous solution of an inorganic detergent. It will be done. Inorganic detergents are preferably inorganic phosphorus-containing compounds such as, but not limited to, phosphates and polyphosphates, particularly preferably trisodium phosphate. Typically, an aqueous solution of 60% trisodium phosphate is used when passing the fiber bundle through the solution, and about 60'C! (14
0"F) to facilitate the removal of organic compounds. Inorganic detergents are in most cases alkaline when dissolved in water, and subsequent plating solutions are generally acidic, so electroplating It is a preferred feature to neutralize the pretreated fibers or bundles with dilute inorganic acids before immersion in the solution.Hydrochloric acid and/or other inorganic acids are suitable in aqueous solutions.

In addition to the pretreatment in step 8, it is possible to eliminate organic compounds from the electroplating R solution, or to reduce only those organic compounds that can be reduced at the cathode surface (which themselves are clean graphite fibers) to liberate the catalyst. The internal presence should be such that throughout plating the graphite or mM surface remains free of organic compound anastomosis. This improvement consists in the strict exclusion of electroplating additives, which are organic compounds such as wetting agents, such as sodium lauryl sulfate, chelating agents, and brightening agents, such as Consists of or includes organic compounds. for example,
Saccharin has a rather unique ability to reduce elemental sulfur at the cathode, so it
in) suitable as modifiers (brighteners).

More specifically, as illustrated in the Y-plane processing section 8, best shown in FIGS. 1 and vS7, the apparatus includes a trisodium phosphate cleaning section 26. It consists of a washing section 30 followed by an acid cleaning section 34 followed by another washing section 38. Pretreatment section 26,3
0.34 and 38 each have a cleaning T-shaped tube 28, as shown in detail in FIGS. 22-24.
．． 32-32A, 36 and 40-40A.

In addition, each pre-treatment section 26, 30, 34 and 38 is
The trisodium phosphate cleaning section 26 and the acid 411i node section 34 have reservoirs into which the discharge waves from the cleaning T-shaped tubes 28.32A, 32.36.40A and 40 enter.
Each has medium-sized tanks 27 and 31. The washing compartments 30 and 38 each have two tanks 33.41 each.
and 39.49. In operation, the fibers 2 pass through the T-shaped tubes 28.32A, 32.36.40A8 and 40 in one direction - the force fluid passes in the opposite direction.

A cleaning solution of trisodium phosphate at an appropriate concentration can be used in the cleaning compartment 26.

However, by implementation, water 3°7q9. Eight ounces per gallon of trisodium phosphate was taught to provide the necessary cleaning of carbon fiber. Water is used in wash section 30 to remove residual trisodium phosphate from fibers 2 exiting section 26.

The fibers then pass through the T-shaped tube 36 in the acid cleaning section 34, with the acid axillary passing in countercurrent to the mfa2. Suitable acids for the cleaning and related pretreatment of trisodium phosphate are:
It is a 10% hydrochloric acid solution. The fibers la2 are then washed with water in a washing section 38, where the water enters through the upper part of the T-shaped tubes 4o and 40A and exits through the upper section of the opening of the T-shaped tubes, which Therefore, it flows countercurrently to the fiber 2.

As seen in FIG. 7, pretreatment zones 8 are interconnected to facilitate pretreatment of the #i fibers 2 and to avoid or minimize accumulation of dyed pretreatment solution. Each pretreatment tank has a tube 308 with a Baskent filter 310 disposed beyond the opening. The liquid discharged from the tank passes through a vertical pipe 308 from various sources to a pump 306.
Sent by. The line 316 from the vertical pipe 308 in the cleaning tank 49 is connected to the T-shaped pipe 40 associated with the cleaning tank 39.
Connect with fluid inlet A. Line 326 is connected to T-shaped tube 40 associated with reservoir 49 and a drain line 320 is provided for draining fluid from reservoir 39.

A ring line 314 extends from the vertical line 308 in the tank 31 to the fluid pipe I of the T-shaped pipe 36 to circulate the hydrochloric acid cleaning solution again. n
1 person to supply the fluid and replenish it! -1 line 324 is provided.

The cleaning tanks 41 and 33 are connected to the T-shaped pipe 3 associated with the tank 41.
2 to the fluid inlet 325 and the standpipe 3 in the tank 41
08 to the T-shape associated with tank 33 + a line 316 to the population of i 32 A. A discharge line 322 is provided for the discharge of υ1 from the tank 33.

The phosphorus sodium trim tank 27 has a C circulation line 312 from the vertical pipe 308 to the T-shaped pipe 28 and a C-circulation line 312 to the T-shaped pipe 28.
It has both lines 300 for supplying and replenishing the initial trisodium phosphate to the fluid population of 8.

Neutralizer 3301 For example, dolomite (Dol.

A neutralization tank 318 supplied with m1te) is provided in this system to receive the hydrochloric acid effluent from the washing tank 39 and to receive the trisodium phosphate effluent from the scour bed 33.

In operation, the fibers 2 are placed in T-shaped tubes 28.32A, 36.
40A and 40, the fluid then exits in one stream from the fluid inlet of the T-shaped tube to the fiber inlet opening of the T-shaped tube. The trisodium phosphate wash solution is recycled through standpipe 308 and internal circulation line 312. The residue of the fibers m2-L: after passing from the single-shaped tube 28 is washed away from the fibers 2 with clean water. Clean water is discharged from the cleaning T-shaped pipe 41 which passes through the T-shaped pipe 32 associated with the cleaning tank 41 and passes through the T-shaped pipe 33A associated with the cleaning tank 33. The fluid in wash tank 33 that becomes pre-dyed with trisodium phosphate is discharged to neutralization tank 318.

After the 1alit2 leaves the wash section 30, the hydrochloric acid wash passes over the fibers 2 in the T-shaped tube 36. T-shaped pipe 3
The effluent from 6 is recirculated to the fluid volume of T-shaped tube 36 via standpipe 308 in tank 31 and recirculation line 314. The fibers 2 leaving the T-shaped tube 36 are washed in a washing section 38.

Clean water enters the wash compartment 38 through the T-shaped tube 40 associated with the wash tank 49 and flows to the wash tank 49. Wash M
Fluid from l tank 49 is routed via line 316 to the fluid inlet of T-shaped tube 4OA associated with wash tank 39 and passes over fibers 2 into wash tank 39. The fluid in cleaning tank 39 becomes contaminated with hydrochloric acid and line 3
20 to the neutralization tank].

The nature of the combination of sodium phosphate and hydrochloric acid with calcium-based materials, such as dolomite, neutralizes the waste and minimizes the additional processing required for the waste before being disposed of via line 328. .

The pretreated m1a2 is then electroplated. As seen in FIG. 1, a plurality of electroplating baths 18
．． 20, 22 and 24 are provided in series. Under the high voltage-high current conditions of this method, electroplating bath 1
8.20.22 and 24 1--row arrangement
Provides a means of providing distinct voltages and currents to the fibers 2 as a function of the accumulation of metal plating on top. Thus, depending on the amount of metal plating on the fiber 2'', the plating 1E current and current can be set to the most appropriate level for the particular resistance developed by the fiber and metal.

The electroplating tank 18 is shown in FIGS. 8, 9 and 10 and is similar in structure to the plating tanks 20, 22 and 24 shown in FIG. Tank 18 is arranged to hold a bath of electrolyte. The tank 18 includes a contact roller 100 and an anode support rod 1 arranged in the circuit.
It is installed together with 02. The contact roller 100 is a bus line l.

4 and the anode support rod 102 is connected directly to the busbar 106. Plating tank 18.20.2
2 and 24 each include a similar, but separate, independent circuit, as seen in FIG. The anode busbar 102 has an anode basket 110 attached thereto. The anode basket 11O is 7N! The grain tanks 18, 20, 22 and 24 are also arranged to hold the current and transfer the current to the nickel or other metal plated chips.
It has 14. Heat exchanger 114 heats the electrolyte bath to reach the desired initial temperature at start-up and cools the electrolyte during high current density operation.

Tank 18 has a reservoir 103 and a recirculation line 109.

M2O3 is defined by a solid wall 105, in which a liquid level controller 107 is provided.

Line 109 contains pump l11 and filter 113 and serves to continuously recirculate the electrolyte from J'+fl l O3 to cell 18. Under normal operating conditions, The circulated electrolyte enters the cell 18, and the electrolyte in the cell is raised to a level above the wall 105 and flows into the 'M4103.'As the electrolyte evaporates from the cell, the liquid level in the bed increases. and requires replenishment from the downstream wash compartment 12 shown in FIG.

Tank 18 also has line 132 and pump 134. Through them the electrolyte flows through the manifold l' 128
sent to. Manifold 128 supplies electrolyte from contact roller 100 to second spray nozzle 130 .

As shown in FIG. 13, the fibers 2 are passed around contact rollers lOO'- and idler rollers 112 located close to the bottom of the bath. The idler rollers 112 are arranged in pairs, around which the fibers 2 move to come into contact with successive contact rollers 100.

Roller Zoo within bath 18 communicates with busbar 104 via contact member 118 . As the detail of contact member 118 seen in FIG. 11 shows, contact member 118 includes a copper rod 120 and a plurality of rows of phosphor.
Formed from bronze fingers 122, they provide positive contact over a sufficiently large area on the contact roller 100 to produce high resistance at the point of contact. Fingers 122 and 124 are resiliently attached to rod 120 and are forced into constant contact with contact roller 100 by the nature of the material.

Thus, high strength positive electrical contact assemblies are provided for environments where ordinary brush contacts do not work well. This is further facilitated by means of protecting the delicate [2] during its passage between the contact rollers. The system includes a recirculating spray system 126, shown generally in FIGS. In fiber Ia2
The spray nozzle 130 is arranged with two parallel tubular arms 136 and 138 located on its surface which bore a nozzle opening 139. As best shown in FIG. 15, one tubular arm 136 of the spray nozzle 130 is
At the point where fiber 2 leaves contact roller 100, jjl
It is arranged to direct the solution tangentially to iAft2.

The other tubular arm 138 of the spray nozzle 130 is.

At the point where the fiber 2 contacts the contact roller loo, it is arranged to supply the electrolyte directly onto a portion of the contact roller lOO. As previously indicated, it is extremely important to ensure that sufficient tension is applied to the fiber M2 to ensure that the fiber 2 is held in a taut straight line between the contact roller ioo and the idler roller 112. . The need for a taut wire is necessary to ensure that a suitably low contact resistance for carrying current exists with high electrical conductivity through the fibers 2 from the contact roller 100 to the IF melting bath. . Contact roller 100 and fiber 2
The electrolyte that recirculates the rainbow provides a parallel resistor in the circuit and serves to cool the fiber 2.

The plated fiber @2 has a low fusing current (fusing c
current), for example, is known to have 10 amperes for a tow of about 7 microns in diameter. However, the method of the present invention requires about 25 amps between contacts or about 125 amps/strand in each bath.

Furthermore, both contact resistance and anisotropic resistance must be overcome. The contact resistance of pure, clean copper, about 7 in H; 12 in chrome, is about 2 ohms, thus requiring 22.5 amps at 45 volts before plating can occur.

The w-directional resistance is i, ooo times that of long sleeves. Thus, the total contact area is 0.8 for the tow diameter [7 microns]
6 cm (0.34 inches)]. By implementation, 1.27 cm (0
, 5 inches) when plating 7 micron tow.
found to adequately meet the electrical requirements of the system;
Therefore 5.08 cm (2 inches) and 7.62 cm
(3 inch) contact roller lOO is used. It is also very important that the contact roller lOO be located at a certain distance L from the electrolyte bath so that the system can be operated at the high voltages required to accomplish this method. In practice, when using a voltage of 16-25 Ports, the contact roller 100 is 1.25 cm from the electrolyte bath.
(0,5 inch) ~2,54 am (1 inch)
It turned out that it should be located somewhere. moreover,
Approximately 0.45m (1.5 feet) to 7.62m (25 feet)
Approximately 7,57 centimeters (2 gallons) per 100 contact rollers traveling in 7 minutes (2 gallons) 7 minutes of recirculation will adequately cool the fibers and provide adequate cooling when more than 5,000 amps of current flows through the system. It has been found to provide a suitable parallel resistor.

The electrolyte in this method is a 60-75% solution (8-75%
10 oz/gal solution) of metal, preferably NiCl
2 and N15Oa. The pH of the solution was set at 4==4.5, and the temperature was set at 6
The recirculation of the electrolyte through the atomizing nozzle 130 at the desired velocity is such that the atomizing nozzle has a temperature of 0,32 cm ( It must be straight f40, 24 cm (3/32 inch) about the center of the 1/1 inch (8 inch).The presence of electrolyte on the 1M fiber is extremely important, but do not remove excess electrolyte. Care should be taken to avoid otherwise the contact roller would become plated in the electrolyte.

The anode support rod 102 of the anode basket 110 is shown in detail in FIG. 20 and consists essentially of three layers. The inner line 150 of #I is the anode basket 110
Provide structural support for Copper coating 152 on steel rod 150
A material 1, such as a steel tube, provides the desired electrical properties for the passage of current, and an insulation material 154, such as vinyl, is provided to insulate the entire anode support rod 102.

At strategic locations on rods 102 and 12, the vinyl is removed and notches 156 expose copper coating 152 to provide electrical contact.

No. 1 (as shown in FIG. 21, the anode basket) 110 has a conventional opening 15B as present in the anode basket, but also has a vinyl insulating cover 162.
The cover extends from the top of the anode bath 110 to a location below the surface of the electrolyte bath. Depending on the practice, insulating the anode Vasquent 110 10.2 to 30.5 cm (4 to 12 inches) from the top protects the anode Vasquent 110 from breakdown of the protective oxide under conditions of high density current and voltage experienced in this method. 110 was found to be protected. A conventional hook 160 present on the anode support rod 110 is positioned to fit within a notch 156 formed in the anode support rod 102. Additionally, the anode basket is made of lIf or titanium due to the high voltage environment and the nature of the electrolyte. The high voltage was found to remove the titanium surface, which is usually the TiO2 layer, from the anode basket 110ft electrolyte to maintenance.

The contact roller 100 is shown in detail in FIGS. 17-19. Each contact roller lOO is located in close proximity to the electrolyte in the plating bath, and each is capable of transporting high current through the system in a high density voltage environment. The contact rollers 100 are thus designed in a continuous arrangement. Contact roller 100 has fixed end forging sections 170 and 172 that hold a cylindrical copper tube 174. A cylindrical copper tube 174 is placed in contact with the commutator fingers 122-123 and to supply current to the electrolyte bath through both fiber #2 and the recycled electrolyte. Copper tube 174 is formed from regular L-shaped copper that must be capable of carrying 350 amps. The diameter of the tube is critical in governing the contact surface for fiber #2 and the distance between the contact roller 100 and the electrolyte surface. In the end, installation 17
0 and 172 are fixedly arranged in alignment and support the tube 174 of the contact roller 100 in an open position. Mounting 170 has a bearing support 176 through which threaded mounting 178 passes. Screw 4 = j178 is copper pipe 1
74 to the bushing support 180, and remove the screw 178 to remove the bushing support 180.
It has the ability to open the copper tube 174 when it retreats.

Handle J172 includes a bushing support 182 in which a detent 184 is formed. Each copper tube 174 has a notch 4-j.
It has an engagement slot 186 which is connected to the detent 1.
84 and the copper tube 174 to the bushing support 1
82, thereby eliminating alignment uncertainties and facilitating shipping on replacement of each tubular section 174.

The entire electrical system 188 of this method! 22, where the voltage and current are applied to each electrolytic cell 18.2.
The installed capacity to supply separately to 0.22.24 is shown. Ordinary rectifiers 189.191.193 and 195
is arranged as a direct current source that supplies current to the respective contact roller 100 of each electrolytic cell. Bus line 10
4.194.196.198 are, by way of example, connected from the respective rectifiers 189.191.193 and 195 to one of the six contact rollers 00 of the electrolytic cells 18.20.22 and 24. It is shown. However, all six contact rollers 100 of each electrolyzer
are connected directly to the same busbar. f()1a106.2
02.204 and J: and 206 are cables 20 from the same rectifiers 189.191.193 and 195, respectively.
8 to the busbar of one WA pole attached to electrolytic cells 18, 20, 22 and 24. Again, each bus bar contacts each anode support rod 102 attached to each electrolytic cell connected to the liI line.

This arrangement results in a separate high voltage for each electrolyzer 1O120
, 22, 24 as a function of the metal plating on the fibers 2 in each electrolytic cell.

Practice has taught that in mass production, the voltage at the fdSl electrolyzer 18 should not be lower than 16 Ports, and is rarely lower than 24 Ports. The voltage at second tank 20 should not be lower than 14 volts, and the voltage at third tank 22 should not be lower than 12 volts.

By way of example, m-fiber 2 was coated in a system of three rectifier-electrolyte bath assemblies, rather than the four shown in FIGS. 1 and 22, under the following conditions, which produced very good coatings: Rectifier 189 191 193 Ampere 1,400 1,400 1,400 Holt 45 26 17 The nickel metallized fiber #n2 produced under these conditions exhibited the following properties and characteristics: Filament round (but Shape of graphite fiber
Depends on the fiber) Diameter: 8 microns Metal coating Approximately 50% of the total fiber mold breakage approximately 0.5 microns thick Harm level: 2.50-3. OOg/am3 Tensile Strength Up to 450,000psi Tensile Modulus 34Mpsi Conductivity 0.008 ohm/cm (,12K+
-C] 0610 ohms/1000 strands/cm After nickel plating occurs, completely plated fiber a
2 is fed to the wash section 12 as shown in FIG.

drag-out section (drag-out 5ecti)
n) 42 and washing compartment 46 are T-shaped tubes 44.44A
, 44B, 48 and 48A, and both neutralize the effluent for discarding waste liquid, and electrolyte bath 18.20.
．． Provides storage for 22 and 24 refills.

As best shown in FIG. 23, drag-out compartment 42 includes separate compartments 252, 254 and 25.
It consists of 6 cascade tanks. Cascade tank is ttA
A three-station cascade countercurrent cleaning tank (Nat
ional PIastics, Thermal El
ectr.

n Djyision). The cascade reservoir automatically provides passage from downstream reservoirs of discharged fluid to the current reservoir by passage around the overflow drum 258. The fluid accumulated in reservoir 256 is transferred to reservoir 256 and reservoir 2.
Between 54 and 25 minutes, reach the level of 10 from the wall 255, tank 2
Go to 54. Similarly, the liquid level in the tank 254 is lower than the separation wall 251.
When the level of the current is higher than the current level of the reservoir 252, the fluid is further drained.

The cleaning section 5 includes tanks 250 and 260. 4f of both
The i250 and 260 have a tube 268 with a /<sket filter 270 located at the top opening.

Conveying line 261 is connected to stand Il' 1268 in tank 260 and has pump 264. Effluent from tank 260 is routed to T-shaped tube 48A associated with tank 250 to wash fibers 2. Effluent from tank 250 is supplied via line 276 to the cascade tank assembly or is disposed of via line 278.

Line 271 connects the drained liquid in tank 252 to tank 18.20.2.
2 and 24, the latter tank being equipped with a liquid level controller 107.

The liquid level controller 107 opens the solenoid valve r273 when the liquid level in the tank 18, 20, 22 or 24 drops to a level that requires electrolyte.

In operation, fiber 2 is inserted into T-shaped tubes 44B, 44A, 44
．． 48A and 48 and washed with water.

Clean water is supplied to the system via line 267 to the T-shaped tube 48, flowing in the opposite direction to the direction of Flt2 and draining into the tank 260 through the upstream end of the T-shaped tube 48. The effluent from tank 260 is sent to the fluid manifold 1 in T-shaped tube 48A, and is discharged from the galvanic coal in T-shaped tube 48A to tank 250. It is relatively dilute as it is present in the tank, and thus it can be discharged as waste through line 278 or fed to tank 256 as needed. Tank 256
．． 254 and 252 are operated continuously in recirculation mode, thereby producing a fluid that becomes increasingly rich in electrolyte. As a result, a minimum amount of contaminated water is generated, while an electrolyte-rich solution is produced for replenishment of the electrolyte and used in the pre-treatment section 8 and the wash section 12 of the system, T-shaped tubes 28 Displayed in , is the 24th ~
It is shown in Fig. 26. As previously indicated, the 1'-shaped tube is designed to provide free flow solution movement with the fibers, I[I2. In the case of installation, the 'r-shaped tube 28 is
It is designed with a 1-flow opening 11210 and a 1-flow opening 212 for the passage of 2-flow. r-shaped tube 2
8 also has a domed housing 214. A solution, such as wash water, can enter the T-shaped tube 28 through this housing 214 and wet Fiber #2 as it passes through the T-shaped tube 28. T-shaped pipe 28
also has a sleeve 216. This sleeve 21
6 creates a pressure point that directs the water in the flow direction. Furthermore, the T-shaped tube is designed with an opening 210 for the passage of the fiber m2 at a height slightly below the opening 212. Thus, the passage of water emanating from the T-shaped tube passes from the delivery tube 218 through the opening 210. The combination of the differential height of the openings 210 and 212 and the presence of the sleeve 216 located in the flow section of the T-shaped tube 28
When am moves in the de-flow direction, ① promotes the movement of the solution in the second-flow direction.

The apparatus of the present invention is arranged to operate synchronously as shown in Figures 27-29. so that the contact roller 100 and the guide roller 51 rotate at the same speed to avoid abrasion of the fibers 2;
A motor 222 is provided.

Motor 222 directly drives an assembly of rollers 223 arranged to act as a capstan. Roller 223 is located within dryer 14 and reverses the direction of #1im six times, as best shown in FIG.

This reversal of direction imparts sufficient force to the fiber to pull it through the device without sagging the fiber.

Furthermore, the motor 222 is coupled by a gear and chain assembly to drive each contact roller 100 and each guide roller 51 at the same speed.

Physically, the gear and chain assembly is the guide drive assembly 225. The contact roller drive assembly 227 is shown in FIG. Each guide drive assembly 225 includes:
It includes a drive transmission gear 230 attached to the shaft 231, a gear 224 firmly attached to the guide roller 51, and a chain 233 engaged with the gears 230 and 224.

The contact roller assembly has a common shaft 2 with gear 230.
31, a gear 241 firmly fixed to each contact roller 100, and both gears 241 and 239 on the six contact rollers 100 associated with each electrolyte bath. Matching chain 24
Contains 3.

As shown in FIG. 30, each guide roller 51
is formed with a groove 28Q extending through a tapered side surface 282 and a flat surface 284. Table+#i 28
The diameter of the guide roller at 4 is the same as the diameter of the contact roller 100 and the capstan roller 223, so that the fiber 2 runs at a constant speed along the path through the device.

The flat surface 284 provides a base for spreading out the fibers or tow 2 and promoting drying or wetting depending on the desired operational effect.

The location of capstan roller 223 within dryer 14 enhances drying. 1L The force applied to the flat surface and the fibers 2 spreads the fibers 4 thereby promoting drying.

The system also includes a variable speed clutch override drive motor 219 for the take-up rule 17. The force generated by this variable torque motor 219 provides the force that pulls the Ia fiber 2 through the system. However, the cabs 97' near-9-223 has a p stage in which the capstan roller -1-2 isolates the direct force applied to the fiber #2 at the winding wheel 17 from the fiber #2 of the t. provide.

The apparatus and method described can not only be used to form electrically conductive fibers, such as metal coatings that are tightly adhered to conductive fibers, such as fibers or graphite, but also It can also be used to form a coating of gold that is firmly adhered to the fibers.

For more information, see Filamen! Table 1r of multiple filaments consisting of only or aimed non-conductive core (1,
Chemical deposition of a thin metal interlayer, sensitized and ultimately tetraelectric, yields a material suitable for plating in the high voltage continuous apparatus and method described above.

According to this aspect of the invention, a metallized filament having a non-conductive core is obtained. In this metal-coated filament, the bond between the coating and the filament is so strong that when the fiber is bent, such as during weaving or knitting, the coating may tear but will not fall off. 1. A core with a smooth surface, such as aramid? When preparing a PL, after roughening the surface, it is necessary to sensitize the roughened surface with a noble metal, such as palladium.

When a rough surface is present, e.g. when using cotton,
111 planes can be omitted. A metal such as Eva, nickel, silver, or copper is then deposited on the rough, sensitized surface. The surface of the sled can be plated with, for example, nickel or silver using an external voltage.

In each case, the surface of the filament is uniform, continuous, and intimate. A square metal coating will form. It is believed that the high voltage provides sufficient energy to cause uniform nucleation, especially when multiple filaments are used. In addition, the high voltage provides a uniformity of 41% on each fiber of the filament, yarn, comprising a thin metal coating on the metallized core according to the present invention.
Cloth, felt, etc., do not remove metal substantially;
Can be tied or folded.

In accordance with this aspect of the invention, a core of a non-conductive polymer having a rough surface sensitized to chemical deposition of metals, and a core of a non-conductive polymer having a rough surface sensitized to the chemical deposition of metals, and a continuous filament consisting of a bonded intermediate layer of conductive metal, alone or in combination with at least one thin, uniform, tightly adhered conductive layer of at least one metal electrodeposited onto said intermediate layer; provided. The bond strength of the coated filament is at least strong enough so that when the coated filament is bent, the coating may break but does not peel off.

More specifically, the core filament is generally selected from 44 polymeric materials, all of which are non-conducting. The material includes polyolefin filaments, such as polypropylene.

Polyacrylonitrile, wool, cotton, rayon, etc.1 For example, poly(ethylene terephthalate) and polyamides, such as nylon, such as poly(caprolactam) and poly(l,6-hexamethylenediamine adipate) and the so-called aramids, which are It is a long chain synthetic polyamide in which at least 85% of the amide bonds are bonded directly to two aromatic rings. is possible. The latter, together with their method of production, are described in the Encyclopedia ao
f Chemical Technology, 3rd
Edition, Volume 3゜John Will
ey, New York, 197g, pp, 213-
242.

Particularly suitable as core material are aramid filaments prepared by polycondensation of dichlorochloride and diamine in amide solvents, such as dimethylacetamide and N-methylpyrrolidone. Such filaments of high strength can be made by solvent spinning the condensation product of p-7 minobennyl chlorite hydrochloride 111, the product is known as poly(p-benzamide) or PPB. There is. Other condensation products are made from p-phenylene diamine and Te1/phthaloyl chloride. It is poly(paraphenylene terephthalamide) or PPD-”I’
known as. Fibers made of the latter are manufactured by DuPont Company, Wt 1ming
ton, Delaware 19898) from trademark KEV
It can be handcrafted with LAR 29 and 49, the latter being a hot drawn fiber. A typical diameter of the filaments used in this invention is 4,000 filaments/bundle, each of the filaments having a diameter of 12 microns.

Referring to FIGS. 31 and 32, the continuous threads and tows used in the core 2 according to the present invention are manufactured by DuPont under trademarks KEVLAR-29 and KEV.
LAR-49 is available, and a suitable polyester M [14DACRO] is available from DuPont.
N Po1yester (Type sa) and manual iI
It is Ding Noh. Suitable nylon polyamide yarns include, for example:
Manpower IIT t#: from DuPont Company (Type
728). Cotton threads and wool fibers can be used. As mentioned above, all such fibers are electrically non-conductive and sensitized to chemical deposition of the metal interlayer 322. Cotton threads and wool fibers are naturally roughened; others must be roughened.

Surface roughening may be carried out by any conventional method, but preferably by polishing the filament with fine silica, aluminum oxide, sand, etc. In a filament of 4 to 15 microns in thickness, for example, 12 will be produced. The roughened surface provides a woody anchorage site for the intermediate layer 3, as shown in FIG. 33, and provides increased mechanical grip. In continuous operation, roughening can be achieved by fluidized bed mechanical polishing means, e.g. Cole-Palmer (Col e
-Parmer type equipment.

Next, the roughened fibers! ? For example, the fibers can be exposed to
l in a solution of soot or tin sulfate! ! The sample is then processed by passing through a solution of the salt of the metal. Wetting of the roughened fibers can be promoted by adding a small amount of detergent in a solution of chloride to soot.

Preferred noble metal salts are water-soluble palladium salts 9 such as palladium chloride. Gold, palladium and rhodium salts can also be used. The sensitized rough surface catalyzes the deposition of metal from ions in the solution used to form the metal interlayer, e.g. the thin layer of metal that catalyzes the deposition of silver metal from silver nitrate, without cleaning. Provided outwardly in a solution of hydrazine, hydrazine compound, or borohydride at a high quinary to low metal ratio, silver ions are reduced to sheet metal that is well bonded to the surface.

The thickness of the intermediate layer 332 increases with time, and is sufficiently thick when the conductivity (or reduction in resistance) is sufficient to make electrodeposition possible in subsequent steps. This can be measured using known methods. Further details regarding this aspect are described in the aforementioned US Pat. No. 3,495,940, but that procedure does not use a roughened surface.

The metal layer 334 has a high voltage as defined above--a high 'rTf
It may be an electrodepositable metal deposited by a flow method. Two or more layers of metal can be applied, and the metals can be the same or different, as shown in the examples.

The roughening of the non-conductive fibers and the subsequent chemical deposition of the metal intermediate layer 334 can be performed as a separate step or can be part of a continuous line plating apparatus as illustrated in FIG. The polishing zone 336.111'' and the intermediate layer deposition zone 3 shown schematically in FIG.
38, 340, 342 and 344 are placed in two layers in the continuous line fitting apparatus shown in FIG. 1, with an intermediate pretreated RP section 8 and a plating section IO.

The metallized filaments of the present invention can be formed into the composite shown in FIG. 34 by conventional means. In FIG. 34, the soot 346 is a plastic, such as an epoxy resin or a phenolic resin, and the soot is reinforced thanks to the metal-coated core 2.

In series there are filament transport sections, e.g. rollers 51.
The components of a continuous treatment system consisting of a fluidized bed mechanical polishing means 336 are shown in FIG. be done. This is not used when the filament has a naturally rough surface. Then, after sensitization by, for example, transfer and immersion 1 in tank 338 holding a 5nC12 solution, washing, then immersion in tank 340 holding P del 2 solution, and washing, the coarse sensitized For example, a filament 2 having a surface of
42 and finally, without washing, into a reducing bath tank 338 containing, for example, hydrazine hydrate (alkaline). A thin silver coating is deposited, to the point that the filament can be used in the composite or, if desired, sent to the plating section 10 of FIG.゛The electrical resistance has been significantly reduced.

As mentioned above, it may be desirable to rinse the metallized fibers produced by the method of the present invention in a post-treatment sizing step. The post-processing sizing step J2 can be carried out independently, but the metallization is carried out as part of the drying step 14 therein as part of the continuous line process shown in FIG. Preferably, the fibers are sized. Post-treatment stage 1 and equipment provide ligneously metallized filaments with sizing agents, eg 1a male. Sizing agents impart various properties to the filament, such as lubricity and bulk, increase the compatibility of the filament with plastic ink, and, when combined with polymers, improve the resistance of the filament. Improves thermal properties.

For convenience, although the following description is made using metal-coated fibers, it should be understood that metal filaments can be treated in a similar manner.

More specifically, as shown in FIG. 40, the sizing and drying apparatus and method includes the steam compartment 55, sizing compartment 366, heating assembly 36 shown in FIG.
4, and a take-up reel 17 shown in section 16 of FIG. As explained hereinafter, the compartment 366 can consist of a medium tank, and one or more heating assemblies 364 can be used. Additionally, means 55 for providing an oxidized surface may be included, such as a low pressure steam box.

As shown in FIG. 40, in one implementation W; ladder, the sizing section 366 is further comprised of a first tank 346, a second tank 348, and a third tank 350, all of which It can contain a solution and can facilitate the passage of a continuous stream of metallized fibers.

Six tanks 346, 348 and 350 have idler rollers 352 and 354 located near the bottom of the tank. Rollers 352 and 354 are cylindrical and guide roller 356 is flat-bottomed to promote tow spreading and uniform sizing.

6 tanks generally have idler rollers 352 and 354
A driven contact roller is positioned above the tank in alignment with the tank. The guide rollers 358 also move left and right to one person in six tanks.

The heating section 364 comprises means for heating the sized metallized fibers to dry and cure the sizing solution or emulsion into metallized carbon fibers. As noted above, the six vessels can have independent subsequent heating sections 364.

Drive means for the assembly is provided by motor 360. The motor 360 directly transmits the drive to the chain tooth 1p assembly composed of the 1 take-up reel 17 and the chain 362, and from there the power is transmitted to the capstan gear 3.
68 to contact roller 358.

In use, metallized H & Fiber 2. The metal coating on the fibers is transferred through the air injection section 53 as shown in FIG. 1 and through the steam box 55 as shown in FIGS. Tank 346 filled with a sizing agent, e.g. aminosilane solution
It is preferable to pass through the After passing through bath 346, the metallized fiber essentially has a coupling/sizing surface bonded to the coated male metal oxide. The fibers 2 are then subjected to bulking/sizing 2 in a bath 34 containing a polyvinyl acetate solution.
8. The polyvinyl acetate solution provides bulk to the metallized fibers in combination with a campling/silicine coating, such as an aminosilane coating. Alternatively, both sizes can be combined in a tank. The fibers, w2, are then fed to a tank 350, which is filled with a size/lubricant, for example a polyethylene solution or emulsion, for fiber lubrication. Alternatively, it can be combined with a sizing/strength, pulling agent and/or sizing bulk density agent in a bath of rl'i-, and the sized fiber m2 is then sent to furnace section 364 where it is dried and cured. , the heated and dried m182 is advanced to the second sizing section 366 and the drying section, and finally wound onto the winding wheel 17. Dual - [mode shown, but for flexibility, depending on the case? Only the to process can be used.

Regarding the cambling/sizing component, this typically consists of a surface-reactive coupling agent. Typically,
Silane, which is a silane or titanate, has the general formula YRStX3, where X is a hydrolyzable group, e.g. alkoxy: Y is a functional organic group.
, such as methacryloxy, epoxy, etc., where R is typically a small aliphatic bond, ~(CH2)n
-, which serves to attach the functional organic group to the silicon (St) at the appropriate position.To illustrate, the silanes that can be manually prepared are: vinyltriethoxysilane, vinyltris (Hetermethoxyeth+S)
Silane, gammamethaxoloxyprobyltokimethoxysilane, beta(3,4-epoxy-cyclohexyl)ethyltrimethoxysilane, comma-glycidoxyprobyltrimethoxysilane, gamma-aminopropyltriethoxysilane, n-beta( 7minoenal) gamma-aminopropyltrimethoxysilane, kammaurei F/ropyltriethoxysilane, gamma-chloropropyltrimethoxysilane, comma-mercaptopropyltrimethoxysilane, etc. Aminosilanes are preferred.

All can be used in pentong brushes and applied in normal media, or diluted with water or organic solvents, or even used as dry concentrates, e.g. in a fluidized bed. Of Noh. Typical th)ates are isopropyl tri(dioctyl pyrophosphate) titanate, titanium di(dioctyl phosphate)oxyacetate-1, and tetraoctyloxytitanium di(dilauryl phosphite).

In practice, for example, gamma-aminopropyltriethoxysilane, e.g.
orning Z-6020, or gamma-grindquinpropyltrimethoxysilane 1 e.g. Dow-C
The orning Z-6040 amide/silane solution has been found to be particularly suitable for coupling Ningel or silver coated carbon fiber or aramid fiber hair aminosilane. Practice has taught that the residence time of the fibers in solution is at least as long as enough to produce a pulled surface. This is typically 0.5 seconds, but this time can be longer, for example about 5 seconds, depending on downstream residence time requirements.

Regarding bulking/sizing agents, this is usually this Li
In terms of f'f, '+lfl, it can be a 41-machine polymer material. Preferably it will be a vinyl polymer or cellulose dissolved in water or an organic solvent; examples of polymers suitable for use are starch, ethers, esters and carboxylates of cellulose. Furthermore, polyvinyl esters such as polyvinyl acetate and copolymers such as ethylene/vinyl acetate, as well as polyvinyl alcohol and dispersants such as polyvinylpyrrolidone can be used. Preferably, polyvinyl acetate is used. All are used in established and well-known venues for sizing purposes.

Depending on the practice, about 20 parts of carboxylated polyvinyl acetate latex (B) per 100 parts of water may also be used.

rden Polyco 2142.50% solids)
Polyvinyl acetate solutions have been taught to provide solutions that are particularly suitable for imparting bulk density to metal plated fibers. The residence time of the fibers in the polyvinyl acetate medium should be at least sufficient to produce a sized surface, and is preferably about 0.5 seconds.

Lubrication is provided by commonly used slip agents or lubricants consisting of organic materials.

Preferably, the molecular film comprises sized fibers and a surface 1 against which said fibers move, e.g.
irgin) plastic pellets. Such characteristics are called hunt-up (han-up).
d-up) and the tendency to wear. Examples of lubricants include fatty alcohols, fatty acid esters, glycerol partial esters, polyesters, fatty acid amides, e.g.
Oleamide, metallic soaps, fatty acids such as stearic acid and polyolefins, especially polyethylene.

Polyethylene is preferred; these can be used in solution and emulsion form.

10 parts of polyethylene (Bercen,
The polyethylene emulsion of Bersize S-200, 50% solids) from Inc. provides a particularly desirable solution for imparting lubricity to fibers. Sufficient fiber residence time is used to generate a lubricated surface.

A time of at least about 5 seconds in the polyethylene medium has been found to be successful.

The method of producing an oxidized surface of a metallized filament generally consists of exposing the outer surface to an oxidizing medium. Of course, metal surfaces are those with +1 oxidation. Chemical or atmospheric techniques, etc., can be used in the case of nickel, tin, copper, brass, etc., and surface oxide coatings can be applied. The use of heating is recommended as it increases the production rate.It is convenient to use air or an oxygen-containing gas as the medium for oxidation and water vapor as the heat source.Metal oxide coatings, preferably Uniform/
Use sufficient time to produce a thin coating. In a continuous process, using water vapor and air, times of only a fraction of a second, e.g. about 025 seconds, are preferred;
Longer or shorter times can be used. For best results, the filament is sized after drying.

The sized and/or oxidized filaments produced in this manner can be chopped
d) Can be used as a material and mixed or compounded with plastics, e.g. nylon, polyester,
They can be mixed or compounded in polycarbonates, polyolefins, polyurethanes, polystyrenes, polyethylenes, etc. in proportions of about 5 to 50% by weight to form 7-trinks composites of fibers and plastics. When the filament is woven, tIIl or mattely laid, the laminate can be 45. It has been found that sized metal-coated carbon #ll fibers can be more easily compounded with plastics without significant difficulty due to the added bulk density of the sized chopped material. Tests have shown that a composite made and cured from 60 parts of silane sized fiber according to the invention and 40 parts by weight of epoxy resin
The short length shear strength at room temperature and high temperature with humidity is approximately 30% superior to that made with unsized fibers.

Fibers sized and/or surface oxidized according to the method of the invention were also woven into fabric patterns. It has also been found that the fuzz that typically extends randomly from metallized fibers does not interfere with weaving after sizing. Additionally, the woven material could be formed into cloth patterns very easily due to the inherent lubricity of sizing materials. Ultimately, sized nickel-coated carbon fibers, graphite fibers, or other high strength fibers have been found to have excellent lubricity, lack abrasion properties, and facilitate weaving. In addition, the sized fibers are
Avoiding irregular fibers extending from the fibers, which can accumulate on guides in machines and the like, thereby accumulating fluff material that significantly disturbs the weaving pattern.

Additionally, the sizing agent acts as a water displacement agent and can be incorporated into the plastic matrices to reduce the tendency of the composite to delaminate from the coated fibers after exposure to moisture.

In practice, carbon fibers coated with nickel and treated with steam, e.g., distilled water, have a dense bond with a thickness of 15 to 50 microns, which is particularly compatible with aminosilanes.
It was taught that it would provide a nickel oxide surface. This is very useful for making composites with polymers that exhibit desired properties.

The following examples further illustrate the invention.

Each piece is made of 7 micron graphite fibers 12.00
4 tows (fiber bundles) of 0 strands at 82-93℃
The solution was drawn continuously through a solution of 479 g/i (8 oz/gal) of Niminatrim phosphate heated to (180-200 T) and then through two wash baths. Second
The effluent from the cleaning tank was returned to the first tank.
, p.

Passed through a neutralization tank containing a 10% aqueous solution of hydrochloric acid (35%) and then through two washing tanks. These two
The effluent from the second of the two wash tanks was returned to the first tank, and the effluent from all tanks was combined for self-neutralization.

In a continuous electroplating system, a plating solution with the following composition was prepared: nickel sulfate (Ni 300g/300g SO, -6
H20) Cis/Charon) Nickel chloride (Ni 90-150g/C12-6H
20) (12-20 oz/caron) Boric acid (Hg, BOa) 37-60g/JJ (5-8
oz/caron) Bath is 60-71'C! (140-160°F) and had a pH of 3.8-4.2.

Four tows (m bundles) of 12,000 strands of 7 microns each were kept in an anode bath filled with electrolytic nickel pellets and stripped of organic contaminants as described above. 5 amps/min/1
,000 strands total λ1! Tow speed of 1.5 m/min (5 ft/min) and 1
20 amperes were drawn continuously through the bath at 6
The voltage drop from anode to cathode was 30 ports. At the same time, the lIi, #I liquid was recirculated through the loop to contact the tow entry and exit passages. The tow was then passed continuously through the same bath at a tow speed of 1.5 m/min (5.0 ft/min) and a current of 180 amps. The life-long acid is composed of a 7 micron fiber core and approximately 50% by weight core-coated fibers with primary deposited crystalline electrodeposited nickel. It was a tow of N strength coated fibers. metal cover 09
was uniform and contained no bare spots.

When a length of fiber was sharply bent and then inspected, there were no circumferential cracks on the metal coating on the tension side of the bend. The first is to prevent the coating from turning into flakes,
Alternatively, it was possible to twist and tie the yarn without dropping it as powder.

- Embossing - Repeat the procedure of Example 1, substituting a tow of graphite fibers through which hot liquid has passed, and in the degreasing chamber 1,1. Electrical condensation of 1-trichloroethane to strip the organic material from the tow produced a uniform, even metal coating.

441! To illustrate the negative effects of compounds, when the concentration of organic impurities in the degreasing chamber of Example 2 was allowed to increase, the organic materials recontaminated the graphite LA and the nickel coating became non-uniform. . The trisodium phosphate cleaning bath in Example 1 was replaced with a wetting agent containing an organic substance (Wyandotte BN Cleaner, 0a
kite 190 cleaning agent or Ivory Li
Quid detergent), the nickel plating was ultimately non-uniform.

Two-length healing side 1 - Continuous tow composed of smooth-surfaced aramid filaments (1 bundle of 4,000 mm, average diameter 12 microns, poly(paraphenylene terephthalamide), DuP
ont KEVLAR49) in a scum fluidized bed with 12 mesh size silica slurried in water.
Each fiber was mechanically polished until the surface was roughened.

10 g/ tow heated to 60°C (140”F)
1 of stannous chloride and 10 ml/liter of concentrated hydrochloric acid, remaining therein for 1 minute and washing. The tow was then heated to 60°C (140'F) with 2.8 g/m of palladium chloride and 10 m
Immerse in an aqueous solution of l/5L of aqueous hydrochloric acid.

One molecule ull was placed therein and washed. This technique was repeated and a rough, sensitized surface was produced on filament 1. Next, 31g/! of tow! ;L
of silver nitrate and then without cleaning,
% aqueous hydrazine hydrate solution (Hummel Ch
chemical Corp. 8, No. 85).

An intermediate layer of silver was thereby deposited in a dense 1-i manner. Specimens were taken, washed, dried, and resistance measured with an ohmmeter. If necessary, the silver deposition procedure is repeated to a resistance of 4 to 66 ohms/m (12 micron tow).
5 yuan to 20 ohms/foot), which at this time was suitable for plating.

In a continuous electroplating system, a plating solution having the following composition was prepared - 1- Nickel sulfate (Ni 300g/ml (40 years old SO4.6)
H20) 90-150 g/f
)-Cl 21+6H20) (12-20 oz/caron) Boric acid (HsBO3) 37-6 og/! ;L(5~8
The bath was heated to 60-71°C (140-160 below) and had a pH of 3.8-4.2.

The anode bath was kept charged with a pellet of electrolytic nickel, and four tows of 4,000 strands of metallized aramid filament, each 12 microns thick, were placed at 1.5 m/1. minutes (5 feet/minute)
draw it continuously through the bath at a speed of
An external voltage of 30 volts was applied using a radio wave of 160 amperes. The pressure drop from the anode to the cathode was 30 ports. At the same time, electrolyte was recirculated through the loop and in contact with the tow entry and exit passages. The tow was then passed continuously through the same bath at a tow speed of 1.5 m/min (5.0 ft/min) and a radio wave of 160 amps. The final product is a high strength composite according to the invention consisting of a 12 micron fiber core, a thin silver interlayer and about 50% by weight of a composite of crystalline electrodeposited nickel tightly adhered to the interlayer. It was a composite fiber tow.

When a length of fiber was sharply bent and then inspected, the metal coating could break, but did not flake off.

[Brief explanation of drawings]

The first [4] excluded the unwinding assembly. 1 is a schematic illustration of the overall method of uninvented continuous electroplating. FIG. 2 is a side view of an unwinding compartment specially arranged to simultaneously supply multiple m#t to an electroplating operation. 3 is a top 11 view of the unwinding assembly of FIG. 2; FIG. FIG. 4 is a cross-sectional side view of the unwind roller assembly. FIG. 5 is a cross-sectional view taken through line 5--5 of FIG. FIG. 6 is an isometric view of the wetting and tensioning rollers between the unwind and the electrolyte bath. FIG. 7 is a cross-sectional side view of the pre-4i11 processing device and related equipment. FIG. 8 is a side view of one electrolytic cell. FIG. 9 is a planar exposure of the tank of FIG. FIG. 1O is a cross-sectional side view taken through line 10--10 of FIG. FIG. 11 is an isometric view of the replacement finger. FIG. 12 is an isometric view of one contact roller associated with the means for providing coolant to the fibers and the current carrying medium from said contact roller to the bath. FIG. 13 is a side view of a compartment of the electrolytic cell depicting the anode basket. Figure @14 is a plan view of the means for supplying electrolyte to the fibers extending from the contact roller to the electrolyte bath. FIG. 15 is a detailed plan view of the nozzle of the spray assembly of FIG. 12; FIG. 16 is a schematic diagram of the electrolyte cooling fluid conduits and contact rollers. FIG. 17 is a side view of the contact roller of the assembly of this method. FIG. 18 shows details of the end cap of the roller of FIG. 17. FIG. 19 is the opposite end of the roller of FIG. 17. FIG. 20 is a partially exploded cross-sectional side view of the anode basket during contact. FIG. 21 is an isometric view of the anode basket of the present invention. FIG. 22 is a diagram of the electrical system of the present invention, and FIG. 23 is a cross-sectional side view of the cleaning tank and related equipment. FIG. 24 is a cross-sectional side view of the cleaning T-shaped tube of the present invention. 25 is a view taken through line 25-25 of the cleaning triangular tube of FIG. 24. FIG. FIG. 26 is a view taken through line 26--26 of the cleaning triangular tube of FIG. 24.6 FIG. 27 is a view of the mechanism for synchronously driving the apparatus of the present invention. FIG. 28 is a 1L diagram taken along section line 28-28 of FIG. 27. FIG. 29 is a side view of the roller assembly in the drying section of the system. FIG. 30 is a cross-sectional view of the guide roller taken through line 30--30 of FIG. 29. FIG. 31 is a schematic cross-sectional view of a metallized rough surface filament of the present invention. FIG. 32 is a schematic longitudinal cross-sectional view of a metal coated rough surface filament of the present invention. Figure fJtJ33 is a schematic enlarged view of Figure 32. FIG. 34 is a schematic partial cross-sectional view of a matrix of metallized filament-reinforced polymer obtained using the present invention. FIG. 35 is a schematic diagram of an apparatus for carrying out the surface roughening and chemical deposition of metal interlayers of the present invention. FIG. 36 is a schematic cross-sectional view of a metal coated m-fiber produced by the improved method of the present invention. Figure 36a is a schematic longitudinal cross-sectional view of a metal sheath manufactured by the improved method of the present invention. Figures 37 and 37a are schematic cross-sectional and longitudinal cross-sectional views, respectively, of a metal-coated core fiber not according to the invention, illustrating non-uniform plating resulting from organic compound contamination; be. FIG. 38 is an enlarged photograph of a metal-coated fiber according to the wood invention, which has a uniform coating due to the formation of a core fiber free of organic compound contamination. FIG. 39 is an enlarged coating of an m-fiber not according to the invention, which has a non-uniform coating due to the use of core fibers contaminated with adsorbed organic compounds. 4014 is a cross-sectional side view of a method and apparatus used for sizing and/or surface toughening metal filament/metal coated high strength fibers; FIG. 2 Fibers, metallized cores, metallized and surface oxidized fibers, sized fibers 3 Intermediate layer 4 Unwinding assembly 5 Guide rollers 6 Tension rollers 8 Pre-treatment zone lO plating equipment 12 Washing station 14 Drying zone, drying process, Dryer 16 Winding section 1 Winding reel 17 Winding reel 18 Tank, electroplating tank, electrolytic tank 20 Tank, electroplating tank, electrolytic tank 22 Tank, electroplating tank, electrolytic tank 24 Tank, electroplating tank, electrolytic tank 26 Trisodium phosphate cleaning compartment 27 tank 28 Washing T-shaped pipe 30 Washing compartment 31 Tank 32 Washing T-shaped pipe 32 A Washing S T-shaped pipe 33 tank 34 Hydrochloric acid compartment, acid washing compartment 36 T-shaped pipe 38 Washing compartment 39 tank 40 Cleaning T-shaped pipe 40A Cleaning T-shaped pipe 6 41 Tank. 42 Cascade tank 6 44 1 character! Cedar pipe 6 44A T-shaped pipe. 44B T-shaped tube. 46 Facial washing section. 48 Cleaning single-shaped tube. 48A Cleaning T-shaped pipe. 49 tanks. 50 sections. 51 Guide roller 9 52 Frame 9 53 Small section, air injection section. 54 Unwinding roller 9 55 Section, steam section, steam box. 56 Rail 9 58 Rail 10 2 Guide roller 4 Compression frame 6 Rod 8 End bearing 0 End bearing 2 Wire 4 Tapered end 6 Screwed end 4 Wetting tab 7 Continuous chain 9 axis 0 Roller [ Fixed tail gear 2kjf variable speed motor 8 th Wheel 5 axis 7 Fiddler roller 0 Roller 102 Anode support rod 103 Gear, reservoir 104 Bus bar 105 Solid wall 106 13I line 107 Liquid level controller 109 Recirculation line 110 Anode basket 111 Pump 112 Idler roller 113 Filter 114 Heat exchanger 118 Contact Member 120 Cup 122 Fin car 124 Fief car 126 Recirculating spray system 128 Manifold 130 Spray nozzle 134 Pump 136 Tubular arm 138 Tubular arm 139 Nozzle opening 150 Steel inner rod 152 Copper coating 154 Insulation 156 Nonch 158 Opening i60 Hook 162 Insulating cover 170 Take-in section 172 Mounting section 174 Cylindrical steel tube 176 Bearing support 178 Screw number 180 Bush support 182 Bush support 184 Detent 186 Slot 188 Overall electrical system 189 Rectifier 191 Rectifier 193 Rectifier 194 Line III 195 Rectifier 196 11 line 198 ノ; J line? 02 (Surface line 204 flvI 206 C7 line 208 Cable 210 1-flow opening 212 D-flow opening 214 Dome-shaped housing 216 Sleeve 218 Delivery pipe 219 BF variable speed clutch/override drive motor, ■Changing torque motor 222 Motor 223 Cap Stun roller 224 Gear 225 Guide drive assembly 227 Contact roller drive assembly 230 Drive transmission gear 231 Shaft 233 Chain 239 Drive transmission gear 241 Gear 243 Chain 250 Reservoir 251 Separation wall 252 Compartment, reservoir 254 Compartment, reservoir 255 Min# wall 256 Interval Chamber, tank 258 Overflow drum 260 tank 261 Conveying line 264 Pump 268 Vertical pipe 270 Filter 271 Line 273 Solenoid brake r 276 Line 278 Line 280 Groove 282 Tapered side 284 ``P-river surface 300 Line 306 Pump 308 \; /l? 310 Basket filter 3 t 2 tif (Ii!i ring line 314 tip
Mill circulation line 6 Line 318 Neutralization tank 320 Discharge line 322 Discharge line 324 Population line 325 Line 326 Line 328 Line 330 Neutralizing agent 332 Intermediate layer 334 Metal layer, metal intermediate layer 336 Polishing section, mechanical polishing means 33 in fluidized bed s
tlJllJI layer precipitation section, cypress, reduction bath 340 Intermediate layer precipitation section, tank 342 Intermediate layer precipitation section, tank 344 Intermediate layer precipitation section 346 Matrix, first tank 348 Second tank 350 Third tank 352 Idler roller 354 Idler roller 356 Guide roller, contact roller 358 Contact roller, guide roller 360 Motor 362 Chain 364 Heating assembly, heating section, furnace section 366 Sizing section 368 Capstan gear patent applicant American Cyanamid Campa drawing engraving (no changes in content) ) in (O ( FIG, 31 FIG, 34 Continuation of page 1 Priority claim ■198 January 2nd [phase] United States)
) [Stock] 5076020198tsubo June 24th [Seo] United States (US) [Stock] 507612■1YC June 24th [
1. Indication of the case Japanese Patent Application No. 59-129911 2. Name of the invention Apparatus and method for continuously plating textiles 3. Relationship with the case of the person making the amendment Patent applicant name American Cyanamid Company 4, Representative 11H 107 6, Drawing subject to amendment 7, Contents of amendment Engraving of the drawing (no change in content)

Claims (1)

[Claims] 1. (a) The fiber is continuously passed through an electrolyte in a tank in which a metal anode is immersed, (b) a direct current is passed through the fiber to the anode, and (C) the electrolyte is immersed in the electrolyte. (d) maintaining a voltage of 16 volts or more from the fiber to the anode across the anode; (d) thereby causing metal to move from the anode to the fiber and bond thereto; ° A method of electroplating fibers, characterized by: 2. (a) DC rectifier, (b) Electrolyte tank from which the rectifier supplies radio waves, (C) Electrolyte in the electrolyte tank, (d) Metal anode in the electrolyte, (e) Fibers in electrolyte (f) Direct current? ! ! 1. An apparatus for metal plating am, comprising: means for supplying an electrolytic solution from a coil through a T#l fiber; (g) means for maintaining a voltage of 16 volts or more between the fiber and the anode. 3. (a) continuously passing the fiber into the electrolyte reservoir over a current carrying surface located above the electrolyte reservoir, and (b) passing the fiber into the electrolyte reservoir at the point where the fiber contacts the current carrying surface and where the cooling fluid is located. A method of cooling a fiber through which an electric current passes, comprising directing a cooling fluid to the fiber at a point away from a current-carrying surface. 4. An electrolyte bath, an electrolyte in the electrolyte bath, a rotating contact roller fixed to the top of the electrolyte bath over which the mat can pass, and a rotating contact roller located at the bottom of the electrolyte bath and in contact with the electrolyte solution in the electrolyte bath. an idler roller placed in alignment with the roller for passing the H&male around it, a rectifier, a 14 wire extending from the rectifier to the electrolyte bath, a conductive bar extending from the bus bar to the contact roller, and a conductive rod extending from the bus bar to the contact roller. an array of conductive finkers extending from a rod and in contact with a contact roller. 5. (a) a pair of contact rollers attached to a portion of the electrolyte bath; (b) a pair of fins attached to the bottom of the electrolyte bath in vertical alignment with said pair of contact rollers; (C) an anode attachment rod attached to the electrolyte bath between the pair of contact rollers; (d) an anode basket depending from the anode body; (e) a reservoir in the electrolyte bath; (f) means for circulating electrolyte from said reservoir to the remainder of the electrolyte reservoir; (g) means for sensing the level of electrolyte in said layer; and (h) means for determining the level of electrolyte in said layer in advance. An electrolyte bath characterized in that it includes a hand for supplying and refilling the electrolyte when at a low liquid level. 6. A first drive motor; a row of rollers arranged as a capstan; a plurality of guide rollers; a plurality of processing rollers, where the diameter of each roller over which the #h fibers pass is . : means for driving the capstan roller, the 1111 guide roller and the 8M roller at the same speed; a take-up reel for the treated fibers; a second drive motor for driving said take-up reel. A device that propels m-fibers through physical processing operations. 7. (a) one stage to pass m fibers through a continuous processing operation; (b) a row of tension rollers around which the fibers pass with a moat that reverses the direction of passage of the fibers; and (C) equal to the speed of the fibers. means for driving said row of tensioning rollers in the same direction as m# at a Trf rate of change or slower than m#. 8. (a) drawing the fiber through the process; (b) passing the fiber through an electrolyte; and (C) at a location upstream of where the fiber enters the electrolyte, equal to or less than the velocity of the fiber. The fibers are tensioned by passing them over a row of rollers selectively driven at a certain speed; A method in which fibers are continuously treated in an electrolytic solution. 9. (a) Pass the fiber continuously over the contacts and into the electrolyte in the bath in which the metal anode is immersed. (b) passing a direct current through the fiber to the anode; and (c) applying tension to [t to ensure a direct, taut path from the fiber at the point of contact with the electrolyte in the cell, thereby A method of electroplating tM#, comprising: transferring and bonding metal to a fiber. (a) DC rectifier; (b) Electrolyte tank to which the rectifier supplies current; (C) Electrolyte in the electrolyte tank; (d) Metal anode in the electrolyte; (e) Electrolyte on the surface of the electrolyte A contact member directly above which is sprayed with electrolyte; (f) means for continuously passing the fibers through the electrolyte; (g) direct current! (h) means for maintaining tension on the fibers to ensure a direct, taut passage from the fibers at the point of contact with the electrolyte in the bath; A device for metal plating fibers, which is characterized by: 11. (a) providing a continuous length of a plurality of conductive graphite core fibers; (b) electrolytically depositing at least one metal on at least a portion of the length of nun; (c) Applying an external voltage between mm and an electrode immersed in said solution while supplying a certain amount of current, said voltage causing the metal to deposit. exceeding the normally required voltage, whereby (i) the metal is reduced on the surface of the fiber and (1
1) The metal nucleates substantially uniformly onto the surface of the fiber,
and (i i i) + iii. a method of producing a coated fiber, wherein a substantially uniform, hard electrodeposited layer is produced on the core-on-core; 1. A method comprising preparing a graphite core fiber substantially free of organic compounds on its surface. 12. A non-conductive polymer core with a rough surface sensitized to chemical deposition of metals, and a conductive metal chemically deposited on the rough surface of the core and tightly bonded thereto. alone or in combination with at least one thin, uniform, tightly adhered electrically conductive layer of at least one metal deposited on said intermediate layer. 13. A core of a non-conductive polymer with a rough surface sensitized to the chemical deposition of metal, and θ of a conductive metal chemically deposited on the rough surface of said core and tightly bound thereto. an intermediate layer, and at least one thin, uniform, tightly adhered conductive layer of at least one metal electrodeposited onto said intermediate layer and bound together without substantial separation and without loss of metal coating. A continuous filament characterized by the ability to 14. (a) providing at least one filament having a continuous length of a coarse, non-conductive polymer core; (b) sensitizing said filament to chemical deposition of metal; ) chemically depositing an intermediate layer of conductive metal firmly adhered to the rough sensitized surface -1- of said filament; and optionally (d) at least a portion of said length of filament;
continuous immersion in a solution in which at least one metal can be electrolytically deposited; and (e) providing an amount of electrical current and providing an external contact between the fiber and the electrode immersed in said solution. applying a voltage, said voltage exceeding the voltage normally required for metal deposition, so that (i) the metal nucleates substantially uniformly on the surface of the filament;
)+if Intermediate Layer A method for producing a continuous filament, characterized in that a substantially uniform, tightly bonded layer of interlayer metal is produced. 15. A core of a non-conductive polymer having a rough surface sensitized to chemical deposition of metal, and an intermediate layer of a conductive metal chemically deposited on the rough surface of said core and tightly bonded thereto. A continuous filament characterized by comprising: 16. Metal filament with sizing agent present on the surface. 17. Metallic filaments containing bulk density characterized by the shape of additional surface material!・. 18. A metal filament containing a surface with considerable lubricity. 19. A metal filament having a metal oxide surface in which a sizing agent is present on the surface. 20. (a) passing a metal filament through a sizing medium; and (b) heating the metal filament to dry and fix the sizing agent to the filament. 8
A method of icing a metal filament with a characteristic. 21. A method for oxidizing a metal filament, comprising passing the metal filament through an oxidizing medium at high temperature until a substantially uniform surface oxide coating is formed on the filament J2.